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Patented Feb. 28, 1933 GUILLAUME DE MONTMOLLIN, JACOB DANUSER, GERALD 0F BASED, SWITZERLAND ASSIGNORS IBASLE, OF BASEL, SWITZERLAND BONHOTE, AND HANS JOHNER, T0 SOCIETY or, CHEMICAL INDUSTRY IN 1 UNSIl'LPHONATED DIAGYLATED nmmims' AND rnoosss'or nKINGsAME No Drawing. Application filed September 22, 1931, Serial No.'564,486, and in Switzerland. September 81.

i The present invention relates to the manufacture of new unsulphonated diacylated diamines. It comprises the process of making these new diamines, and the new products themselves.

It has been found that new unsulphonated diacylated diamines of the benzene series may be produced by condensing an aliphatlc or an aromatic diamine with an unsulphonated hydroxycarboxylic acid ofthe benzene series which is so substituted that it couples with diazo-compounds in ortho-position to ,the OH-group. Such acids are those in which the para-position to the OH-group is occupied by a substituent. As such acids there may for example be named the p-hydroxy-benzoic acid, the cresotinic acids OH:-CH :COOH=1:4:2, "1:3:4, 1:4:3, 1 :2: 4, the xylenolcarboxylic acids OH:CH3:CH3:COOH=1:4:5:2,

1:3:5:4,1:2:4:5,1:3:6:4,monalkylethers of the dihydroxybenzenecarboxylic acids, such as 0 113 OH: OCH COOH= 1: 3:4, 122:4,1z4z3, etc.

The products so obtained, which correspond to the general formula wherein each benzene nucleus carries an'OH- I group, and wherein in each benzenevnucleus the para-position to the OH-group is substituted, and finally wherein R and R mean II or alkyl, and R an aliphatic oraromatic radicle, such products being for example the following:

GW- WTQ V 1 H o I 1 3 CH: 7 i V I i d 0 TF FOiQt o 11 H H CH3 CH3 are soluble in caustic alkalies and have a more or less pronounced afiinity for vegetable fibers, so that they are absorbed by the fibers and can then be 1 developed by means of various diazo-compounds (among others those referred to Y in U; S. Patents Nos.

\ 1,034,853, 1,453,660, and 1,457 ,114) to produce i 7 excellent brown dyestufis.

used as mordants for basicdyestufls'whereby valuable dyeings are produced. i v

Various primary and secondary diamines can be used'for the condensation. For 111- stance ahphatlc dlamlnes such as ethylene or aromatic diamines such as diamines, ortho-, par a-, or meta-phenylene diamines, toluylene diamlnes, 1nonoa lkyl-' or symmetrical dialkylphenylene diamines, diaminonaphthalenes, diaminodiphenylmethanes and their analogues and homologues, diamino benzenes, diaminodiphenylamines, diaminocarbazoles, azoxyanilines, diaminoanthraquinones, diaminodiaryls, such as benzidine, tolidine, dianisidine or I diphenetidine, diaminodiaryl'ureas, diaminodiphenyltriazines, diaminodiarylimidoxazoles, imidthiazoles or the like.

azoxytoluidines,

They may 'also be diaminodiarylimidazole s, diaminodiaryl- The condensation may be conducted in any known manner suitable for making amides.

The following example illustrates the invention: V I

7 6 parts by weight of para-cresotinic acid of the formula fiooon 1 CH3 and 64 parts of dianisidine are introduced into 550 parts of toluene, and into the mixture, at about 90 6., there are the course of about hour, 34c parts of phosphorus triehloride. The temperature is then raised gradually to 110 C. and main-, tained thereat for some hours.-

The mixture is then miXed with an excess of sod um carbonateand toluene is blown 0s with-steam.

The residue is filtered, the solid matter.

washed with water and purified by dissolution in dilute caustic soda solution, filtration and precipitation by addition of acid to the filtrate. When dry the product is a grey white powder. It can be crystallized from chlorobenzene. It forms fine bright scales,

melting at 274.276 C. The product corresponds very probably with the formula 7 OH OH ll 1 0 H I H O 0 CH3 H30 0 CH3 CH3 3 The corresponding product from benzidine of the formula on r p p on M a t 1% CH3 I H I I 3H3 melts with decomposition at a 330-333 C., and the o-tolidine derivative of the formula II I V l II o H H o 7 CH3 H3O v v CH3 CH3 1 also melts with decomposition at 280- named above.

In like manner the operation may ,be con-r ducted with other diamines, such asthose Instead of toluene basic sol- Vents maybe used, for instance'diethylaniline.. In this case the reaction mass maybe worked up by introducing it in a 'dilute acid and then purifying the separated diarylide dropped '1 the para-position to the OH-groupi's'substi- 1 formula in known manner, for example by dissolution in caustic alkali solution and cautious precipitation with acids.

Also other acids may be hydroxy-benzoic acid. What we claim is 1. Process for the manufacture of unsulphonated diacylated diamines of the genused, such as paracral formula wherein each benzene nucleus carries an-OH- and wherein in each benzene nucleus tuted by an alkylor alkoxy group, R and R meaning H or'alkyl, and R meaning an aromatic radicle, consisting 1n causing two molecular proportions of such unsulphonatwhereinoR R and R have the above men tioned significations'.

2. Process for the manufacture ofunsul- V phonated diacylated diamines of the general formula wherein each benzene nucleus carries an 011-,

group, and wherein in each benzene nucleus the para-position to the OH-group is substituted by an alkylor alkoxy group, R standing for a radicle of the diphenyl series, consisting in causing two molecular proportions of such unsulphonated hydroxycarboxylic acids of the benzene series in which theparaposition to the OH-group is occupied by a substituent, to react, in presence of dehydrating agents and in the heat, on one'molecular proportion of a diamine of the diphenyl serles.

3. Process for the manufacture of unsulphonated diacylated diaminesof the general wherein each benzene nucleus carries an 011- group,-and wherein in each benzene nucleus the para-position tothe OH-group substituted by an alkylor alkoxygroup, consistin in causing two molecular proportions.

of such unsulphonated hydroxycarboxylic acids of the benzene series in which the araposition to the OH-group is occupied y a substituent, to react, in presence of dehydrating agents and in the heat, on one molecular roportion of benzidine.

4. rocess for the manufacture of an unsulphonated diacylated diamine of the formula F i l u on H 0 CH: CH3

consisting in causingtwo molecular proportions of paracresotinic acid to react, in presence of dehydrating agents and in the heat, on one molecular proportion of benzidine.

5. Process for the manufacture of unsulphonated diacylated diamines of the general formula wherein each benzene nucleus carries an OH- group, and wherein 1n each benzene nucleus the para-pos1t1on to the ()H-group is substituted by an alkylor alkoxy group, consisting in causing two molecular proportions of such unsulphonated hydroxycarboxylic acids of the benzene series in which the paraposition to the OH-group is occupied by a substituent, to react, in presence of dehydrating agents and in the heat, on one molecular proportion of orthotolidine.

6. Process for the manufacture of an unsulphonated diacylated diamine of the for consisting in causing two molecular proportions of paracres-otinic acid to react, in presence of dehydrating agents and 'in the heat,

on one molecular proportion of dianisidine.

7. As new products the unsulphonated diacylated diamines of the general formula wherein each benzene nucleus carries an OI-lgroup, and wherein in each benzene nucleus the para-position to the OH-group is substituted by an" alkylor alkoxy group, R and R meaning H or alkyl, and R meaning an aromatic radicle, which products are soluble in caustic alkalies, have a pronounced afiinity for vegetable fibers when in solution in dilute alkalies, react with diazo-compoundsywith formation of azo-dyestuffs, and are split by saponifying agents into diamines and such hydroxycarb-oxylic acids of the benzene series invwhichthe'para position to the OH- groupis occupied by a substituent.

8. As new productsthe unsulphonated diacylated diamines of the general formula wherein each benzene nucleus carries an OH- group, andwhcrein ineach benzene nucleus thehpara-posltion to the oH-vgroup is substituted by an .alkylor alkoxy group, which products form bright, powders, are solublein caustic alkazlies, have a pronounced affinity for vegetable fibers when 111 solut on 1n dilute alkalies, react w1th diazo-compounds with formation of 2120' dyestufis, and are split by saponifying: agents into benzidine and" such hydroxycarboxylic acids of thebenzen'e series in which the para-position to the OH- group is occupied by'a'substituent. I 9. As a new product the unsulplionateddiacylated diamine' of the'formula 1 which product is soluble in caustic alkalies, has a pronounced aflinity for vegetable fibers; when, in solution in-dilutealkalies, reacts with diazo-compo'unds-with formation of azo-dyestuffs, and is split by sap-onifying agefiits into benzidine and para-cresotinic ac1 "T10; As new products the unsulphonated diacylated diamines' of the general formula 4 o N Nee .g p e l CH3 wherein each benzene nucleus carries an OH- group, and wherein in each benzene nucleus 7 p the para-position to the OH-group is substiacid. In witness whereof we have hereunto signed our names this 15th day 11. As a new product the unsulphonated n diacylated diamine of the formula (1)11 I V (|)H t i l t CH3 CH 7 CH3 CH:

which product is soluble in caustic alkalies, has a pronounced aflinity for vegetable fibers when in solution in dilute alkalies, reacts with diam-compounds with formation of azo-dyestuifs, and is split by saponifying agents into ortho-tolidine and para-cresotinic acid.

12. As new'products the unsulphonated diacylated diamines of the general formula QOEYOQWF 6 H O v CH3 0 CH wherein each benzene nucleuscarries an OH- group, and wherein in each benzene nucleus the para-position to the OH-group is substitutedb y'an alkylor alkoxy group which products form bright powders, are soluble in caustic alkalies, have a pronounced aflinity for vegetable fibers when in solution in dilute alkalies, react with diazo-compounds with formation of azo-dyestufl's, and are split by saponifying agents into dianisidine and such hydroxycarboxylic acids of the benzene series in which the para-position to the OH-group is occupied by a substituent.

13. As a new product the unsulphonated diacylated diamine of the formula OH on I a I t i i l) (50113 7 oom CH CH3 which product is solublein caustic alkalies,

has, a pronounced affinity for Vegetable fibers when in solution in dilute alkalies, reacts with diazo-compounds with formation of azo-dyestufi's, and is split by saponifying agents into dianisidine and para-cresotinic GUILLAUME DE MONTMOLLIDL; JACOB DANUSER. I n

GERALD. BONHOTE." HANs JOHNER.

of September,- 

